Process for resolving petroleum emulsions



Patented Apr. 11, 1939 STATES OFFHC PROCESS FOR RESOLVING PETROLEUM EMULSIONS Melvin De Groote, University to The Tret-O-Lite Company,

City, Mo., assignor Webster Groves,

Mo., a corporation of Missouri 4 Claims.

This invention relates to the treatment of emulsions of mineral oil and water, such as petroleum emulsions, and has for its object to provide a novel process for resolving or breaking petroleum emulsions of the water-in-oil type into their component parts of oil and water or brine.

The treating agent or demulsifying agent employed in the present process is a new composition of matter consisting of a certain kind of amine salt derived from water-soluble petroleum sulfonic acid, or acids of the kind hereinafter described. Said new material or composition of matter may be used either alone, or in admixture with conventional demulsifying agents, such, for example, as demulsifying agents of the modified fatty acid type, or of the alkylated aromatic sulfonic acid type.

Another object of my invention is to provide a novel process for resolving or breaking petroleum emulsions of the water-in-oil type.

Petroleum sulfonic acids are produced from a wide variety of petroleum distillates or petroleum fractions and in some instances they are produced from the crude petroleum itself. When produced from crude petroleum itself it is customary to use crude oil of the naphthene type, crude oil of the paramn type, crude oil of the asphaltic type and mixtures of said three different types of crude oil.

The art of refining crude petroleum of various fractions, using sulfuric acid of various strengths as well as mpnohydrate and fumingacid, is a well known procedure. In such conventional refining procedure, petroleum sulfonic acids have been produced as by-products. For instance, in removing the olefinic components, it has been common practice to use sulfuric acid so as to polymerize the olefines or convert them into sulfonic acids which are subsequently removed.- Likewise, in the production of white oil or highly refined lubricating oils, it has been customary to treat with fuming sulfuric acid so as to eliminate certain undesirable components.

In recent years, certain mineral oil fractions have been treated with sulfuric acid with the primary object of producing petroleum sulfonic acids, and in such procedure the petroleum sulfonic acids represented the primary objects of reaction rather than concomitant by-products.

Petroleum sulfonic acid, regardless of whether derived as the principal product of reaction or as a by-product, can be divided into two general products,to-wit,green acid or acids and mahogany acid or acids. The green acids are characterized by being water-soluble or dispersible. In

other words, they form either true solutions or sols. For purpose of convenience, they will be herein referred to as water-soluble without any effort to indicate whether the solution is molecular or colloidal in nature. The green acids as indicated by their name frequently give an aqueous solution having a dark green or grey-green appearance. They generally appear as a component of the acid draw-off and do not remain behind dissolved in the oil fraction which has been subjected to sulfuric acid treatment. The green acids are not soluble in oil even when substantially anhydrous, and certainly are not 501 ble in oil when they contain as much as 15% of water. Similarly, their salts obtained by neutralizing the green acids with a strong solution of caustic soda, caustic potash, or ammonia, are not oil soluble. For convenience of classification the ammonium salt will be considered as an alkali salt. .0 In contradistinction to the hydrophile green acids, there occurs as in the manufacture of medicinal white oil, the oil soluble type or the ma- 7 hogany acids. These mahogany acids are characterized by being soluble in oil, especially when anhydrous, and being soluble in oil even if they contain some dissolved water. Some of the mahogany acids also show limited hydrophilic properties to the extent that either some water can be so dissolved in the acids or they in turn may dissolve to some extent in water. In some instances their salts, such as the sodium, ammonium, or potassium salt, will dissolve in water to give a colloidal sol. However, regardless of the presence of any hydrophilic properties whatsoever, they always have a characteristic hydrophobe property, as indicated by the fact that the substantially anhydrous form, for instance. their alkali salts containing 5-12% water, will, dissolve in 'oil. This clearly distinguishes them from the green, acids previously referred to, because the green acids in similar form containing the same amount of water, for example, will not dissolve in oil. The green acids as such are essentially hydrophilic and non-hydrophobic in character. 45 The utility of the mahogany acids in various arts has been enhanced by increasing their water solubility; for'instance, converting the mahogany acids into hydroxy alkylamine salts. On the other hand, as far as I am aware, no valuable product of commerce has resulted from decreasing the water solubility of the mahogany acids by the addition of some oil soluble basic amine, such as, for example, triamylamine. The triamylamine salts of mahogany acids, for example,

which the alkali salts may have exhibited and show, as ,would be expected, an increased solubility in hydrophobe solvents.

Green acids are hydrophile in character as previously stated. Their hydrophile character has been increased by neutralization with materials such as triethanolamine and the like. Such green acid 'salts having enhanced water solubility as compared with the ordinary alkali salts, have found application in certain arts.

I have found that if green acids, that is, the oil-insoluble type, are neutralized with an aralkyl amine so as to produce a water-insoluble product, the resulting material, even though it does not exhibit any marked oil solubility, especially when it contains -l0%-of water, still has pronounced value as a demulsifier for oil field emulsions, either when used. alone or when used in conjunction with other known demulsifying agents. I have found that sometimes such amine sale of green acids will mix in with a hydrophobe material and hydrophile material so as to produce a homogeneous mixture. The eflectiveness of the above described material or composition of matter as a demulsifying agent for oil field emulsions appears to be related to some factor other than its solubility characteristics.

The new composition of matter above described, which is employed as the demulsifying agent in my process is represented by the aralkylamine salts of hydrophilic non-hydrophobic green petroleum acids as exemplified by the benzylamine salt. The manufacture of said new composition ,of matter involves nothing more or less than neutralizing the selected petroleum sulfonic acid with a suitable amine until neutral to methyl orange indicator, or otherv suitable indicator. For purpose of convenience, I prefer that the selected petroleum sulfonic acid contains not over 15% of water. It is understood, of course, that the conventional procedure employing double decomposition instead of direct neutralization,

can be employed in the manufacture of my new' material or composition of matter. For instance, the sodium salt of the selected petroleum sulfonic acid can be dissolved in alcohol and the amine hydrochloride added so that sodium chloride will precipitate. After filtering off the precipitated sodium chloride, the alcohol can be evaporated and the amine salt recovered. If desired a mixture of amines instead of a single amine, may be employed.

It is known that benzylamine can be derived from benzyl alcohol, which is CsH5.CH2OH, or phenyl carbinol (phenyl methyl alcohol). One, of course, can have various homologues of this alcohol obtainable by substitution either in the ring or in the side chain. Phenyl ethyl alcohol or phenyl methyl carbinol, which is an isomer of phenyl ethyl alcohol, can be converted into the corresponding amines. Various substituted benzyl alcohols are known (see Textbook of Organic Chemistry, Bemthsen, 1933, p. 452). Such substituted benzyl alcohols can be converted into the corresponding amines, so as to yieldsubstituted phenyl alkylamines or phenyl alkylamines; methyl or dimethyl benzylamine may be reacted with a suitable chlorltydrin.

Reactions of the kind just referred to, that is, involving a suitable chlorhydrin, may involve ethylene chlorhydrin, propylene chlorhydrin, glycerol chlorhyrin, etc. Similarly, the aryl group that is introduced need not be monocyclic but atom is always through an alkyl carbon atomchain. For reasons of economy and ready availability, I prefer to use benzylamine as the most desirable aralkyl amine.

It may be well to point out that hydrophile non-hydrophobe petroleum sulfonic acid or acids of the green acid type vary somewhat; for instance, the molecular weight may vary within the range of 350-500 or thereabouts. Naturally these petroleum sulfonic acids may carry some polymerized olefines, free hydrocarbons, or the like, or may even carry a bit of naphthenic acids which represent carboxylated non-sulfonated petroleum acids. As previously stated, these materials are well-known commercial products and are available in the open market either in the form of the acid itself orin the form of a salt.

The amine above described may properly be referred to as'basic, inasmuch as its basicity is in the neighborhood of that of ammonia or triethanolamine. In some instances the basicity may be somewhat greater or perhaps slightly less. In order to insure such basicity it is necessary that there be no aryl or aromatic radical attached to the amino nitrogen atom, In other words, such materials as phenyl benzylamine, diphenyl benzylamine, naphthyl ethyl benzylamine, etc; are not satisfactory because due to the presence of the aromatic phenyl radical or aromatic naphthyl radical or any aryl radical attached directly to the amino nitrogen atom, the basicity of the amine is reduced to that of aniline or the like. Such amines of low basicity do not form stable salts with the petroleum acids of the kind described. The term sulfonic acid used in the claims, is intended to mean and refer to a substance that consists either of a single acid or a mixture of acids.

Briefly described, my process consists simply in subjecting the emulsion to the action of a demulsifier consisting of the above described new material or composition of matter. Said material is used either alone or in admixture with another or with other conventional demulsifying agents and its method of use is the same as that generally employed in resolving or breaking petroleum emulsions of the water-in-oil type with a chemical demulsiiler. In conformity with conventional practice, the demulsifier may be introduced into the well in which the emulsion is produced; introduced into which the emulsion is flowing; orint'roduced the demulsifier into a tank in which the emulsion is stored. .After treatment the emulsion is allowed to stand in a quiescent state, usually in a settling tank and usually at a temperature varying from atmospheric temperature to about 200 F., so as to permit the water or brine to separate from the oil, it being preferable to keep the temperature lowenough to prevent the volatilization of valuable constituents of the oil. The amount of demulsifier that may be required to break the emulsion may vary from 1 part of demulsifler to 500 parts of emulsion up to 1 part of demulsifier to 20,000 or. even 30,000 parts of emulsion. The new composition of matter that is employed as the demulsifier in my process, constitutes the subject-matter of my divisional a conduit through arouse application Serial No. 256,780, filed February 16, 1939. 7

Having thus described my invention, what I claim as new and desire to secure by Letters Patent is: v

1. A process for resolving petroleum emulsions of the water-in-oil type, characterized by subjectingthe emulsion to the action of a demulsifler comprising a water-insoluble salt of an aralkyl amine of the End characterized by the absence of an aryl radical as a substituent for an amino hydrogen atom, said amine being obtained from water-soluble non-hydrophobe petroleum'suli'onic acid of the green acid type.

2. A process for resolving petroleum emulsions of the water-in-oil type, characterized by subfleeting the emulsion to the action of a demulsifler comprising a water-insoluble salt of an 1 amine; said amine being characterized by the fact that no amino hydrogen atom has been substituted by any radical other than an I radical; and said amine saltbmng ob- Patent No. 2,155,?) 5- MELVIN DE GROCTE,

4. A process for resolving petroleum emulsions of the water-in-oil type, characterized. by subjecting the emulsion to the action of a demulsifler comprising a water-insoluble salt derived from benzylamine and water soluble non- A from water-soluble'non-hydrophobe pe-l hydrophobe petroleum sulfonic acid of the green acid type.

mvm DE GROO'I'E.

CERTIFICATE OF CORRECTION.

April 11, 19 9,

' It is hereby certified that error' appears in the printed specification of the above numbered patent requiring correction as follows; Page 2, first column, line 22, for "sale" readsalt; same page,-"seoond column, lines 58 and 59 strike out the words "the denulsifier"; and that the said Letters Patent shouldbe read'with this correction therein that the same may con form to the record of the case inthe Patent Office.

Signed and sealed this.l3th day r June, A. b 19 9...

"(Sea1) Henry Van Arsdale Acting Commissioner of Patents. 

